Noncrystaujne resin product



PatentedJan.

' UNITED STATES across: NosoaYs'rALLmr: ansm raonno'r Torsten Basselstrom, Savannah, GI", aslignor to G. and A. Laboratories, Savannah, Ga, a corporation of Georgia a No Drawing. Application September 29, 1937,

Serial No. 166,443

z Claims. :(01. 260-91) This inventionrelates toanimproved detergent, wetting agent and noncrystalline resin product and process oi producing the same.

Many detergents and wetting agents are 5 known, ior example, soaps, sulionated castor oil, suliated higher iatty alcohols oi the higher iatty acids, sulionated higher iatty acids, etc, 01 these, soaps sufier from the disadvantage oi being precipitated from their aqueous solutions by the electrolytes in hard water, particularly by waters carrying calcium compounds, and the sulfated higher iatty alcohols, and the sulionated higher fatty acids suiier iromthe disadvantage of high cost oi the higher alcohol used, so that their used in trade has been severely limited.

2 The product in accordance with my invention possesses superior detergent and wetting powers, is economical to manufacture, requires no complicated separation and isolation of the raw material to be sulionated and may be made by a very simple sulionation process and apparatus. The calcium salts oi my improved detergent are not precipitated in hard water.

Broadly speaking, my invention comprises the 25 product oi the sulionation oi a resin known to the trade as Hyex resin and prepared in accordance with the process disclosed'ln United States Patent No. 2,154,629 oi April 18, 1939, to Edwin E. Littmann entitled Process ior the treatment 30 oi abietyl compounds and products produced thereby.

.Said Patent No. 2,154,629 discloses the treatment oi compounds containing the hydrocarbon nucleus of abietic acid so as to decrease their ap- 35 parent unsaturated character, and possibly increase their melting points and improve their color, and also relates to the treated products so;

formed. Said treatment comprises contactin the abietyl compound with a catalyst oi the type 40 hereinafter described, in a manner adapted to exclude the possibility of reaction between the abietyl compound and any other material. As a result oi such treatment, a change in the chemical and physical properties oi the abietylcom- 45 pound, believed tobe due to a simultaneous dehydrogenation and hydrogenation by the heating oi the abietyi compound 'in' the presence oi the hydrogenation catalyst only, e. g. palladium takes place and the resulting product willbe found to have.a greatly decrease apparent color.

The catalysts which may be used in eiiecting this change or intraor intermolecular rearrangement are those which catalyze the hydrogenation oi unsaturated organic compounds, ior example, any oi the nickel, platinum, palladium or copper chromite catalysts used in such hydrogenation. Preierably a palladium catalyst will be employed in the method according to this in- 0 vention, ior example, a catalyst comprising 40% by weight oi palladium supported on fibrous as-,'

bestos.

Desirably, the abietyl compound and the catalyst will be brought into contact at an elevated,

temperature, in order that a practical reaction rate may be obtained, but the use of an elevated temperature is not necessary ior the accomplishment of the desired results. The optimum temperature range for the most satisfactory results is from about 150 C. to about 250 0. Since thorough contact between catalyst and abietyl compound can best be obtained when the abietyl compound is in liquid or vapor phase, the abietyl compound, when not a liquid at the temperature employed, will be heated to render it liquid.

It is essentialthat the treatment of theabietyl compound be carried out in such a manner that no reaction can occur between the abietyl compound and any other material. No added hydrogen is present during the treatment. While the treatment may be carried out in the presence of air, it is preierable to treat the abietyl compound in an. atmosphere of more inert gas, ior example, carbon dioxide, nitrogen, etc.

The iollowing table shows comparative values oi various chemical constants for treated and untreated abietyl compounds:

1" rosin, "1" main, beiore sitar treatment treatment Thiocyanate No 90-06 -14 Melting point, drop method -C. 80-85 86 90 Color. Slightly bleached Sa'poniiication N04 168-172 167-171 Oxygen absorption pageant oi total absorbed by 2 doub e nds ..pereent.. 40 1 D l The decrease in the thiocyanate number and in oxygen absorption exhibited by the treated 1" rosin is proof or the marked decrease in apparent chemical unsaturation produced by treatment in accordance with this invention. The iact that the saponification number is practically the same ior both treated and untreated rosins is prooi that the carboxyl groups oi the rosin acids have been unchanged by the treatment, which must, thereiore, aiiect the hydrocarbon nucleus only.

More specifically, my invention comprises the sulionation by treatment by concentrated suliuric acid of wood or gum rosin which has been simultaneously dehydrogenated and hydrogen ated by heating in the presence 0! a hydrogenation catalyst, e. g. palladium, in accordance with the process disclosed in Patent No. 2,154,629, and ii desired sulionation oi the resin dissolved in a solvent thereior which is unattacked or attacked by the sulfuric acid, e. g. carbon tetrachloride,

liquid sulfur dioxide, petroleum distillate, or unsaturated hydrocarbons and/or alcohols of the aliphatic, alicyclic and/or aromatic type.

As sulfonating agent I preferably employ sulfuric acid of specific gravity about 1.84, although Imay employ somewhat lower strengths of sulfuric acid or somewhat higher strengths, even to fuming sulfuric acid or sulfur trioxide, but at the slight disadvantage of reduced yields of monosulfonic acids, because of side reactions and/or formation of disulfonic acids or mixtures thereof. I may also employ, if desired, chlorosulfonic acid as my sulfonating agent.

Example I As an example of the carrying out of my process, 100 g. of the Hyex resin described above were finely pulverized and added gradually to 200 cc. of sulfuric acid of specific gravity 1.84

at a temperature of 10 C. with vigorous stirring. The temperature of the mixture rose to 371 C., but there was no evolution of sulfur dioxide. Sulfonation was complete in 45 minutes, and the temperature dropped to 5 C., due to the surrounding ice bath used. The mixture was then poured into ice and the nearly colorless precipitate collected, washed with cold water of 223-4 C. (with decomposition), [a]n=+71'.72,

in a yield of 50 g. The yield of the brownish, insoluble product was 47 g. This insoluble product may be'used as a grease-setting agent or, after removal of acid bodies by digestion with aqueous alkali, and crystallization of the residue from acetone, yields a solid melting at about 13l.5 C. to 132 C. From the alkaline extracts of the brownish, insoluble product, an additional 10-20% or more of Hyex sulfonic acid can be recovered by acidification. The noncrystalline material, remaining after the removal of these crystalline constituents. I have found to be useful, after refining, e. g. by fractional distillation, as a superior rosin oil in the manufacture of printers ink, plasticizers, and the like.

Example 11 In a further example of the carrying out of my invention, 10 g. of the Hyex resin acid obtained by fractional crystallization of Hyex resin, and having a melting point of about 156-158" C. and

1 an optical rotation [aln of about +3.83, was

sulfonated at 10 to 15 C. with '75 cc. of sulfuric acid in a period of 30 minutes, with vigorous stirring. The pale orange solution resulting was poured into ice water, the precipitate collected, washed with cold water, extracted twice with boiling water, leaving about 2 g. of insoluble material. The combined aqueous extracts, on acidification by 10 cc. of concentrated hydrochloric-acid, precipitated 7.2 g. of a sui fonic acid melting at 220-3 C. (with decomposition) [a]n=+61.33, recrystallized from glacial acetic acid, melting at 2233-2245 C. (with decomposition) Example III In a further example of the carrying out of a,aso,oss

for about 10 minutes, and the two layers sepa-' rated while still warm. The carbon tetrachloride layer was again extracted with water by refiuxing. The yield of sulfonic acid obtained from the aqueous extracts was 35%. Evaporation of the carbon tetrachloride layers left a light colored resin similar to the raw material treated.

-My sulfonic acid product will be found variously adaptable to uses as an improved detergent and wetting out agent, e. g. in the scouring of textiles, as a soap assistant,.etc

I may prepare the neutral or acid alkali or alkaline earth, or organic base, e. g. ethanolamine, salts of my sulfonic acid product, and

The mixturewas then poured into 2 liters of water, the mass refluxed,"

such also are variously adaptable to uses as improved detergents and wetting out agents.

The noncrystalline, brownish material separated irom the sulfonic acid, as shown, for example, in Examples 1 and 2, I have found useful as a grease-setting and/or emulsifying agent, e. g. in the manufacture of cup grease, solid oils, and the like.

Example IV As an example of carrying out my process of making a cold set grease, the noncrystalline, brownish material separated from the sulfonic acid, as shown, for exam'ple, in Examples I and II, was dried to about constant weight. Seven and one half grams of this dried material was dissolved at about 130 C. in 22.5 g. of mineral oil of about sec. viscosity (Saybolt) at 100 F., after cooling, the solution was saponifled at room temperature, of about 25 C., with '10 g. of mineral oil, 100 sc. viscosity (Saybolt) at 100 F., containing 25% of suspended calcium hydroxide and stirred for about 10 sec. to about 2 minutes to form a grease.

This application is a continuation in part of my application, Serial No. 70,672 for Detergent and wetting agent and process of producing the same, filed by me March 24, 1936, and .now issued as Patent No. 2,121,033 of June 21, 1938.

What I claim and desire to protect by Letters Patent is:

1. The crude, noncrystalline brownish, insoluble product obtained by treating a mixture of dehydrogenated and, hydrogenated resin with concentrated sulfuric acid under conditions which promote sulfonation, and removing the sulfonic acid by aqueous extraction.

' absence of added substances capable of reducing the degree of unsaturation of the rosin under the conditions of treatment, and removing the sulfonic acid by aqueous extraction. 

